Hydrogenation of detergent alkylate



July 8-, 1969 H. E. JACOBS ET AL HYDROGENATION OF DETERGENT ALKYLATE Filed April 10, 1967 BROMINE NUMBER KLETT COLOR OF $03 SULFONATE o o 2 2 on o m Sheet of 3 500psxe /KLETT COLOR TEMPERATURE 300 REACT OR TEMPERATURE ,500 pa s I I I BROMINE NUMBEi 1 Vs TEMPERATURE REACTOR TEMPERATURE F INVENTOR. JOHN cuwsrmu HARRY E. JACOBS GEORGE R mamas/r55 W/fdw ATTORNEY July 8, 1969 JACOBS ET AL 3,454,666

HYDROGENATION OF DETERGENT ALKYLATE Filed April 10, 1967 Sheet 3 of s I80 KLETT COLOR V5 TE MPERATURE I60 I40 120 KLETT COLOR OF $0 SULFONATE IOO 40 e0 80 100 I I REACTOR TEMPERATUREF I 0.|2 a: BROMINE NUMBER 5 0.10 5 2 TEMPERATURE D Z 0.08

DJ E 0.06 g 0: 0.04 CD 40 so I20 I40 REACTOR TEMPERATURE F INVENTOR- JOHN c. JUBIN, JR. HARRY E. JACOBS GEORGE RMASOLOGITES /ZL/FZEZ ATT RNEY United States Patent US. Cl. 260674 11 Claims ABSTRACT OF THE DISCLOSURE A process for the selective hydrogenation of a detergent alkylate material in order to improve its color and odor characteristics wherein alkenylaryl compounds and poly-nuclear aromatic compounds contained as impurities in said detergent alkylate material are selectively hydrogenated, while the mono-nuclear alkylaryl compounds also contained in said detergent alkylate material do not undergo hydrogenation but retain their aromatic character, comprising contacting said detergent alkylate material in a contact zone with a hydrogen-containing gas in the presence of a catalyst at a temperature in the range of from about 50 F. to about 200 F., at a pressure in the range of from about 5 p.s.i.g. to about 50 p.s.i.g. and at a liquid hourly space velocity in the range of from about 0.5 to about 3.

BACKGROUND OF INVENTION This invention relates to the selective hydrogenation of detergent alkylates (materials containing major amounts of mono-nuclear alkylaryl compounds), and as impurities, minor amounts of alkenyl substituted aromatic compounds and poly-nuclear aromatic compounds. More specifically, this invention relates to the selective hydrogenation of the impurities contained in the detergent alkylate material without substantial conversion hereof of the mono-nuclear alkylaryl compounds in order to produce a product suitable for use in the production of detergents and wetting agents with improved color and odor characteristics.

For approximately the past two decades, alkylaryl sulfonates have been extensively used in synthetic detergent compositions; at the present time the bulk of the commercial detergent compositions are based on this type of surfactant. As a starting material for the preparation of the alkylaryl sulfonates, there are generally utilized detergent alkylates comprising a major amount of alkylaryl hydrocarbons whereby said alkylaryl hydrocarbons can be sulfonated in order to produce the detergent composition. Heretofore, prior to sulfonating the detergent alkylate material, the various impurities contained therein which afiect the detergent quality have been removed by various treatments. More particularly, the detergent alkylate has been subjected to acid treatment to remove impurities which ar responsible for its malodor and poor color stability, followed by a clay treatment to neutralize and decolorize the alkylate. These prior art techniques have not, however, proved to be entirely satisfactory or economical in that such methods have resulted in Significant product losses. Additionally, the prior art methods have required large capital expenditures in order to construct commercial size plants, and have further required facilities to dispose of large quantities of used acid and clay.

In accordance with our invention the disadvantages of the prior art techniques are avoided and there is now provided a method whereby a detergent alkylate material can be subjected to a selective hydrogenation treatment Patented July 8, 1969 in order to remove impurities and thereby improve its odor and color characteristics.

SUMMARY OF INVENTION In accordance with our invention a detergent alkylate material is subjected to a selective hydrogenation treatment in order to produce a product wherein impurities have been removed, and whereby the odor and color characteristics of said product are substantially improved as compared to the untreated detergent alkylate. More particularly, in the method of our invention, the detergent alkylate material is contacted with a hydrogen-containing gas in a contact zone in the presence of a catalyst at a temperature in the range of from about 50 F. to about 200 F. and at a pressure in the range of from about 5 p.s.i.g. to about 50 p.s.i.g. and at a liquid hourly space velocity of from about 0.5 to about 3.0.

The untreated detergent alkylate generally has a bromine number of approximately 0.1 to approximately 0.6, although bromine numbers as high as 1.5 have been encountered. However, following the hydrogenation treatment of our invention, the bromine number is reduced to less than 0.1, generally to less than 0.06. In addition, the untreated detergent alkylate, when subjected to SO, sulfonation, has a Klett color in excess of 200, whereas subsequent to hydrogenation, the product, when subjected to sulfonation, has a Klett color less than 200, generally less than 100. The improvement in bromine number and Klett color which provides a measure of product quality, i.e., odor and color characteristics, as compared to the untreated detergent alkylate is apparent. Further, in view of the low pressures employed, i.e., pressures less than 50 p.s.i.g., hydrogenation of the mono-nuclear aromatic ring compounds is minimized, whereby the hydrogenated product when subjected to S0 sulfonation will have a low unreacted oil content.

It is therefore an object of our invention to replace the prior art acid treating and clay filtration methods with a selective hydrogenation treatment thereby avoiding the necessity of disposing of large quantities of used acid and clay.

It is another object of our invention to provide a method for the selective hydrogenation of a detergent alkylate material in order to produce a product having improved odor and color characteristics.

It is yet another object of our invention to provide a method for improving the odor and color characteristics of a detergent alkylate material without significantly effecting the mono-nuclear alkylaryl compounds contained therein or the alkylaryl sulfonates produced therefrom.

A further object of our invention is to provide a method for the selective hydrogenation of alkenylaryl compounds and polynuclear aromatic compounds contained in a detergent alkylate material while the mononuclear alkylaryl compounds also contained in said detergent alkylate material do not undergo hydrogenation but retain their alkylaryl character.

Other objects, advantages and features of our invention will be apparent to those skilled in the art without departing from the spirit and scope of our invention, and it should be understood that the latter is not necessarily limited to the accompanying discussion.

In a broad aspect our invention relates to a method of improving the odor and color characteristics of a detergent alkylate material containing alkylaryl compounds, alkenylaryl compounds and polynuclear aromatic compounds comprising contacting said detergent alkylate material with a hydrogen-containing gas in a contact zone in the presence of a catalyst at a temperature in the range from about 50 F.. to about 200 F. and at a pressure in the range of from about 5 p.s.i.g. to about 50 p.s.i.g.

In a more limited aspect our invention relates to a method of improving the odor and color characteristics of a detergent alkylate material obtained from either the directalkylation of an aromatic hydrocarbon with an alkyl chloride (obtained from the chlorination of a straight-chain paraflin) or with an olefin in the presence of an aluminum chloride catalyst wherein said detergent alkylate material contains as impurities alkenylaryl compounds, and polynuclear aromatic compounds comprising contacting said detergent alkylate material with a hydrogen-containing gas in a contact zone in the presence of a catalyst at a temperature in the range of from about 50 F. to about 200 F. and at a pressure in the range of from about p.s.i.g. to about 50 p.s.i.g.

In the more limited aspect of our invention, the utilization of mild hydrogenation conditions, i.e., temperatures in the range of from about 50 F. to about 200 F. and pressures in the range of from about 5 p.s.i.g. to about 50 p.s.i.g. is particularly suitable for the hydrogenation of detergent alkylate materials produced from either the direct alkylation of an aromatic compound with an alkyl chloride in the presence of an aluminum chloride catalyst or from the alkylation of an aromatic compound with an olefin in the presence of an aluminum chloride catalyst.

It is known to those skilled in the art that alkyl chlorides can be prepared by the chlorination of a straight chain paraffin. However, it is not known how to limit the introduction of only one atom of chlorine into one molecule of the alkane in the chlorination procedure, and yet convert a substantial portion of the alkane present. As

such, both monochloroalkanes and polychloroalkanes are i produced. Further, as the extent of chlorination is increased the selectivity with respect to the formation of monochloroalkanes is decreased. Since the mono and polychloroalkanes and unreacted alkanes cannot be readily and economically separated from each other, the total chlorination product is generally used in the alkylation of aromatic compounds.

When the total chlorinated product obtained as hereabove set forth is reacted with the aromatic compound, various compounds are produced, which when subjected to hydrogenation at high temperatures, i.e., temperatures in excess of 200 F., results in the removal of chlorine from the chloroalkanes thereby forming additional alkenylaryl compounds which as previously indicated, adversely affects product quality. Further, the chlorine when removed from the chloroalkanes reacts with the catalyst thereby forming a chlorinated catalyst, said chlorinated catalyst tends to initiate undesirable side reactions which further affect product quality. In the method of our invention however, in view of the low temperatures employed, these problems are avoided.

It will be apparent to those skilled in the art that a generally similar relationship obtains in the alkylation of an aromatic compound with an olefin in the presence of an aluminum chloride catalyst, i.e., various chloride complexes are formed which, when subjected to hydrogenation at high temperatures results in the formation of alkenylaryl hydrocarbons.

The product obtained from the selective hydrogenation of the detergent alkylate material can be sulfonated and neutralized in a manner known to those skilled in the art to produce alkylaryl sulfonates suitable for use in the production of detergents and wetting agents.

DESCRIPTION OF DRAWINGS In order to more fully understand the method of our invention, reference is made to the accompanying drawings wherein:

FIGURES 1 and 2 are charts showing the relationship of Klett color of the S0 sulfonate and bromine number of the hydrogenated detergent alkylate material as a function of reactor temperature in the range of from about 100 F. to about 300 F. (palladium on carbon catalyst),

FIGURES 3 and 4 are charts showing the relationship of Klett color of the S0 sulfonate and bromine number 4 of the hydrogenated detergent alkylate material as a function of reactor temperature in the range of from about 40 F. to about 120 F. (palladium on carbon catalyst),

FIGURES 5 and 6 are charts showing the relationship of Klett color of the S0 sulfonate and bromine number of the hydrogenated detergent alkylate material as a function of reactor temperature in the range of from about 70 F. to about 120 F. (palladium on alumina catalyst).

PREFERRED EMBODIMENT In accordance with our invention the process conditions of temperature, pressure, liquid hourly space velocity and hydrogen-containing gas rate are inter-related such that the combined feed and hydrogen-containing gas, as it initially contacts the catalyst bed, consists of a gas phase and a liquid phase wherein the liquid phase comprises substantially all of the charge to a reaction zone. The process conditions are further maintained within such limits as to avoid the hydrogenation of the mono-nuclear aromatics, and further to avoid the production of additional olefins. The reaction is carried out under relatively mild conditions to accomplish the aforesaid purpose.

The desired results are obtained at the preferred operating conditions hereinafter set forth.

Although in the method of our invention the temperatures employed can be maintained in the range of from about 50 F. to about 200 F., it is preferred to maintain the temperature in the range of from about F. to about F. for the following reasons: As previously indicated, the utilization of temperatures less than 200 F. results in bromine numbers of less than 0.1 and Klett colors of a product when subjected to S0 sulfonation less than 200. As temperatures are decerased below 200 F. the bromine number and the Klett color of the S0 sulfonate likewise decrease. However, as further decreases in temperature occur below approxiamtely 120 F. to 80 F., dependent upon the nature and activity of the catalyst, the bromine number and Klett color of the S0 sulfonate start to increase. Nevertheless, such increases in bromine number and Klett color of S0 sulfonate resulting from such further decreases in temperature are within an acceptable limit, i.e., bromine numbers less than 0.1 and Klett colors of S0 sulfonate less than 200.

The pressure is maintained within the range from about 5 p.s.i.g. to about 50 p.s.i.g. It is preferred, however, to maintain the pressure within the range from about 5 p.s.i.g. to about 25 p.s.i.g. The method of our invention is effected at any suitable liquid hourly space velocity. It is preferred, however, that the space velocity (LHSV-volume of hydrocarbon mixture being hydrogenated per volume of catalyst per hour) be maintained in the range from about 0.5 to about 3.

The hydrogen-containing gas present in the reaction zone can be obtained from any suitable source, such as for example a reforming process or other refinery source and it need not be entirely pure. It is preferred, however, that the hydrogen-containing gas contain at least 70 percent by volume of hydrogen. The hydrogen-containing gas can be partially or totally recycled within the process of our invention, and if desired, purification means can be utilized to remove contaminants from the gas before recycling back to the reaction zone. Excessive pressures are avoided in order to avoid conversion of the mono-nuclear aromatic compounds to other derivatives, thereby increasing the unreacted oil content of the sulfonated product.

The catalyst used in the present invention must be one having specific characteristics that make it particularly suitable for the process of our invention. The catalyst must eifect the desired reactions at the low temperatures and pressures hereinabove set forth so that the reactions take place in the desired manner without forming additional olefins or causing hydrogenation of the mono-nuclear alkylaryl aromatic compounds.

Suitable catalysts for the hydrogenation reaction include nickel on a support, for example, alumina (preferably 5 to 15 weight percent of nickel expressed as elemental nickel), platinum or palladium on a support, for example, alumina or carbon (preferably 0.1 percent to 5 percent weight of platinum or palladium expressed D alkylaryl compounds for detergent and wetting agent manufacture.

Our invention will be more fully understood by reference to the following examples.

In the examples hereinafter set forth the detergent as the element), cobalt and molybdenum oxides on a 5 alkylate feed streams having the following compositions support; for example, alumina (preferably 1 percent to and properties, and herein designated as Feed A and 5 percent weight cobalt oxide expressed as C and Feed B, were hydrogenated. percent to 25 percent weight molybdenum oxide expressed TABLE I as M00 or tungsten and nickel oxides or sulfides (pref- V01 u me Percent erably containing tungsten and nickel in the ratio of 3:1 to 10:1 by weight) Component Feed A Feed B The preferred catalyst of our invention is one which Paraflins Trace Trace. consists essentially of palladium supported on a suitable Xfgjfggfgggfi 92 base, such as for example carbon and inorganic oxides CHHeH-MIndrJ STHdYeY 6.2 Such as alumina, silica, boria, magnesia, zirconia, etc. 8:3 2 g g fi i f gt? 8%: or mixtures thereof including silica-alumina, silica-alu- Hen-1.}(Acenaphthen'fiiiZfibhfiifli: 0.11--

Trace. mine-magnesia, silica-zirconia, titania-zirconia, etc. We gfg ff' have discovered that a particularly suitable and preferred Percent chlorine (Indenes) '11: 80-90 p.p.m I 115 ppm catalyst for effecting the desired reaction of our invention gig g gf ffgf ff 3 33 gig: is a catalyst having from about 0.05 percent to about 10 n percent by weight of palladium deposited on the surface Volume P unreacted 011 (pfedomlnantly paratfins) f alumina or carbon, r f bl f about to 1 1n material produced when feed streams subjected to 80;, percent of palladium. The catalyst can be prepared in the sulfontlonl form of spheres, pellets or a powder, depending upon the Percent type of process in which it is used. Spheres, however, are Feed A 0.6 preferred. Feed B 0.3

The method of our invention may be effected in either The f d Streams were analyzed by means of a mass speca batch or continuous type operation in any suitable trometer to determine their compositions. manner such as in a fluidized bed reaction zone, in a fixed A detergent alkylate feed stream f the composition bed reaction Zone, It is Preferred, however, that the set forth in Table I was directed to a reaction zone conl'eaction be Carried out in the liquid Phase in a fixed bed taining a vertical catalyst bed. The feed was passed upupfiow reaction zone although downfiow operation is also Wardly through the catalyst bed cocurrchtly with a suitable. The use of the fixed bed system is preferred since drogen stream Th temperature, pressure, h d fl it requires the lowest Capital eX'Ptinditum and can be P- rates, and liquid hourly space velocity were maintained erated substantially without catalyst losses. In operation at the values shown in the Examples 1 through 9. The of an upflow fixed bed reaction system the liquid deterfeed (A or B), catalyst weight, bed height and volume gent alkylate feed material and hydrogen is fed co-currentare also shown in the examples.

Example Feed B B B B B B A A A Temperature, F 79 79 103 224 251 298 171 200 342 Pressure, p.s.i.g 6 25 25 200 200 100 430 430 430 LHVS 1 1 1 1 1 1 1.2 1.0 1.1 S.c.f. Hg/bbl 590 610 650 125 125 5 90 77 97 BromineNo 0.04 0.06 0.04 0 26 0.09 Klett color of S03sulfonate 78 73 70-80 620 400 165 Unreacted oil in sulfonate,

Volume percent 1 1 1 2.1 2.1 4.9 6 Catalyst height 10").

2 1% palladium on 18-20 mesh alumina spheres (weight 71.8 gms., volume 100 00., bed

height 10%") 3 0.5% palladium on alumina pellets (weight 101 gms., volume 100 00., bed height 1y upwardly through a catalyst bed in order to obtain the desired degree of hydrogenation. The temperature, pressure and space velocities are maintained within the ranges hereinabove set forth.

As can be seen from the conditions of temperature and pressure set forth, the hydrogenation is conducted under relatively mild conditions, i.e., temperatures less than 200 F. and pressures less than 5-0 p.s.i.g. We have discovered that the mild conditions employed results in a product having a low bromine number and when subjected to S0 sulfonation, a low Klett color, i.e., a product having improved odor and color characteristics. Increased severity results in high bromine numbers and high Klett colors of the S0 sulfonate.

We have additionally discovered that the use of the mild hydrogenation conditions does not significantly increase the percent unreacted oil in the product as compared to the untreated detegent alkylate material.

The hydrogenation treatment of the detergent alkylate thus improves the color and odor characteristics of the product which is particularly desirable when producing As can be seen from Examples Nos. 1-9, the process in acordance with our invention when conducted under mild hydrogenation conditions, i.e., low temperatures and pressures, results in a product having substantially improved bromine numbers and Klett colors of the S0 sulfonate. Examples Nos. 1-3 conducted at temperatures less than about 120 F. and pressures less than about 50 p.s.i.g. result in bromine numbers of 0.06 and lower, and Klett colors less than with substantially no increase in the unreacted oil content of the sulfonate. Whereas, as can be seen from Examples Nos. 4-9 the reaction at high temperatures and pressures, i.e., temperatures above 200 F. and pressures above 50 p.s.i.g. result in a product having bromine numbers in excess of 0.06 and Klett colors in excess of 100. Further, the high temperature and pressure conditions result in increased unreacted oil content of the S0 sulfonate as is clearly seen in Examples 5, 7, 8 and 9.

The effect of the temperature and pressure on the Klett color of the S0 sulfonate and the bromine number of the detergent alkylate is clearly apparent from FIGURES 1-6. In FIGURES l and 2 various runs were made with Feed B at temperatures in the range of from about 100 F. to about 300 F. and at pressures from about 25 p.s.i.g. to about 850 p.s.i.g. The catalyst was 1 percent palladium on carbon, the liquid hourly space velocity was 1, and the s.c.f. H /bbl. was maintained in the range of from about 200 to about 700 s.c.f. H /bbl. 47.3 grams of catalyst having a volume of 100 cc. forming a 10%" bed was utilized in an up-fiow reactor. It is apparent from FIGURES l and 2 that decreases in temperature and pressure result in lower Klett colors and lower bromine numbers.

Additional runs were made with Feed B utilizing a 1 percent palladium on carbon catalyst at temperatures from about 60 F. to about 120 F., and at pressures of 5 p.s.i.g., 25 p.s.i.g. and 200 p.s.i.g. The weight of catalyst, catalyst volume and catalyst bed height was the same as that used for FIGURES 1 and 2. The liquid hourly space velocity was maintained at 1 and the s.c.f. H /bbl. was maintained at about 500 s.c.f. H /bbl. As temperatures are reduced from about 120 F. to about 60 F. the Klett color of the S sulfonate and the bromine number of the detergent alkylate increases. However, within this particular temperature range the Klett colors and bromine numbers as shown in FIGURES 3 and 4 are within the preferred range of our invention. The curves are based upon the composite data of all of these runs.

FIGURES 5 and 6 are based upon runs with Feed B and a 1 percent palladium catalyst on alumina spheres. The catalyst weight was 68.6 grams with a volume of 100 cc. maintained in a 10" bed. An up-flow reactor was utilized. The s.c.f. of H /bbl. was maintained at about 500 s.c.f. Hg/bbland the liquid hourly space velocity was maintained at about 1.0. As can be seen in FIGURES 5 and 6 lower pressures and temperatures result in substantially reduced Klett colors and bromine numbers.

The examples hereinabove set forth with the accompanying figures indicate that the odor and color characteristics of the detergent alkylate material can be substantially improved through the selective hydrogenation method of our invention, i.e., the bromine numbers are reduced to less than 0.1 and the Klett color of the S0 sulfonate is reduced to less than 200.

The apparatus which can be used in carrying out the present invention is not critical. Any conventional hydrogenation equipment can be used. It is only necessary that the equipment be capable of withstanding the pressures and temperatures of the reaction and that the equipment be designed in accordance with sound engineering practice.

It will be apparent to those skilled in the art that there is provided a process for the hydrogenation of a detergent alkylate in order to improve its odor and color characteristics. It will be further apparent to those skilled in the art that the hydrogenation is achieved without significantly afiecting the other properties of the alkylate or finished detergent.

It will be understood that various modifications of the invention will become apparent and can be made by those skilled in the art without departing from the spirit and scope thereof, and that the specific details hereinabove set forth are purely illustrative.

Having thus described our invention, it should be understood that no undue limitations or restrictions are to be imposed by reason thereof.

We claim:

1. The method of improving the odor and color characteristics of a detergent alkylate material containing mono-nuclear alkylaryl compounds, polynuclear aromatic compounds and alkenylaryl compounds comprising contacting said detergent alkylate material in a reaction zone with a hydrogen-containing gas in the presence of a catalyst at a temperature in the range from about 50 F. to about 200 F. and at a pressure inthe range of -from about 5 p.s.i.g. to about 50 p.s.i.g.

2. The process according to claim 1 wherein the catalyst is palladium on a carbon support.

3. The process according to claim 1 wherein the temperature is maintained in the range fromabout F. to about F. and pressure in the range from about 5 p.s.i.g. to about 25 p.s.i.g. and the liquid hourly space velocity is maintained in the range of from about 0.5 LHSV to about 3.0 LHSV.

4. The process according to claim 3 wherein the catalyst is palladium on an alumina support.

5. The process according to claim 3 wherein the catalyst comprises 0.1 to 1 percent by weight palladium deposited on an alumina support.

6. The process according to claim 5 wherein said contacting takes place in the liquid phase.

7. The process according to claim 6 wherein said detergent alkylate material and said hydrogen is passed co'currently upwardly-through said contact zone.

8. The process according to claim 6 whereby the bromine number ofsaid detergent alkylate material is reduced to less than 0.1 and whereby the Klett color of said detergent alkylate when subjected to S0; sulfonation is reduced to less than 100.

9. The process according to claim 1 wherein said detergent alkylate material is prepared from the direct alkylation of an aromatic compound with an alkyl chloride.

10. The process according to claim 1 wherein said detergent alkylate material is prepared from the alkylation of an aromatic compound with an olefin in the presence of an aluminum chloride catalyst.

11. The process according to claim 9 whereby said detergent alkylate material and said hydrogen is passed cocurrently upwardly through said contact zone.

References Cited UNITED STATES PATENTS 9/ 1961 Favis.

3/1965 Pappas et a1 260-667 

